Exercise

Structure of glasses

Christian Certa
[email protected]
Sphere Packings

trigonal planar
tetrahedral octahedral cubic

3 0.155 4 0.225 6 0.414 8 0.732

icosahedral dodecahedral
𝑟𝑐𝑎𝑡
𝑟𝑎𝑛
12 0.902 20 1.803
2 of 12 Lecture: Mineral Materials I | Dr. Philipp Jacobs | Chair of Glass and Glass-Ceramics | WS 2024/2025
Exercise: Structure of glasses
Contact: Christian Certa, M.Sc. | Forckenbeckstr. 33 | Tel.: 0241/8047980 | E-Mail: [email protected]
Sphere Packings
trigonal planar

tetrahedral octahedral cubic

3 0.155 4 0.225 6 0.414 8 0.732

icosahedral dodecahedral

𝑟𝑐𝑎𝑡 Calculate the coordination polyhedra

𝑟𝑎𝑛 for cation-oxygen sphere packs listed
below from the ionic radii [nm].
12 0.902 20 1.803

Si4+ Al3+ B3+ P5+ Mg2+ Ca2+ O2-

0.041 0.054 0.025 0.038 0.072 0.100 0.140

3 of 12 Lecture: Mineral Materials I | Dr. Philipp Jacobs | Chair of Glass and Glass-Ceramics | WS 2024/2025
Exercise: Structure of glasses
Contact: Christian Certa, M.Sc. | Forckenbeckstr. 33 | Tel.: 0241/8047980 | E-Mail: [email protected]
Sphere Packings
trigonal planar
icosahedral dodecahedral
tetrahedral octahedral cubic

3 0.155 4 0.225 6 0.414 8 0.732 12 0.902 20 1.803

Si4+ Al3+ B3+ P5+ Mg2+ Ca2+ O2-

0.041 0.054 0.025 0.038 0.072 0.100 0.140

𝑟𝑐𝑎𝑡
0.293 0.386 0.179 0.271 0.514 0.714
𝑟𝑎𝑛

tetrahedral tetrahedral trigonal tetrahedral octahedral octahedral

planar

4 of 12 Lecture: Mineral Materials I | Dr. Philipp Jacobs | Chair of Glass and Glass-Ceramics | WS 2024/2025
Exercise: Structure of glasses
Contact: Christian Certa, M.Sc. | Forckenbeckstr. 33 | Tel.: 0241/8047980 | E-Mail: [email protected]
Glass structure (short and mid range order)

Glasses have a short-range

order and a mid-range order.
But NO long-range order.

Crystals have
short- and long-range
order

5 of 12 Lecture: Mineral Materials I | Dr. Philipp Jacobs | Chair of Glass and Glass-Ceramics | WS 2024/2025
Exercise: Structure of glasses
Contact: Christian Certa, M.Sc. | Forckenbeckstr. 33 | Tel.: 0241/8047980 | E-Mail: [email protected]
Elemental behaviour in glasses

Network formers
• form a polymerised network
• in oxide glasses, Si, B and P are
among the network formers

Network modifiers
• modify the network of the network
formers
• formation of non-bridging oxygen in
the network
• in oxide glasses, the elements of the
alkali and alkaline earth metals are
among the network modifiers

6 of 12 Lecture: Mineral Materials I | Dr. Philipp Jacobs | Chair of Glass and Glass-Ceramics | WS 2024/2025
Exercise: Structure of glasses
Contact: Christian Certa, M.Sc. | Forckenbeckstr. 33 | Tel.: 0241/8047980 | E-Mail: [email protected]
Elemental behavior in glasses

Structurally active elements

• form charge deficit tetrahedra

• Charge balance by (earth) alkali ions
• If no charge balance can take place, they act as network modifiers
• In oxide glasses Al is the most important structurally active element (but also Be, Ga, In, ... belong to this
group)

→ can (co-)form or modify network

7 of 12 Lecture: Mineral Materials I | Dr. Philipp Jacobs | Chair of Glass and Glass-Ceramics | WS 2024/2025
Exercise: Structure of glasses
Contact: Christian Certa, M.Sc. | Forckenbeckstr. 33 | Tel.: 0241/8047980 | E-Mail: [email protected]
Calculation of Q-value (NBOs) based on glass composition
Oxide Mass-% Mol-% Element Amount (mol) Molar Masses [g∙mol−1 ]:
SiO2 68 70.4 Si4+ 70.4 SiO2 = 60.08
Na2O 9 9 Na+ 18 Na2O = 61.98
CaO = 56.08
CaO 13 14.4 Ca2+ 14.4
Al2O3 = 101.96
Al2O3 10 6.1 Al3+ 12.2
∑ 100 99.9 Mass−%
Mol−% = Molar Mass
Mass−%
σ
Molar Mass

Tetrahedra = charge deficit tetrahedra + network former

= 12.2 + 70.4
Charge Deficit Tetrahedra 12.2
NBO/T-ratio 0.42 Q-Value 3.58
Non-bridging oxygens 34.6 molar amoun ts molar amoun ts
molar amoun ts

NBO = positive charges of network modifier – charge deficit tetrahedra

= (18 + 2*14.4) - 12.2

8 of 12 Lecture: Mineral Materials I | Dr. Philipp Jacobs | Chair of Glass and Glass-Ceramics | WS 2024/2025
Exercise: Structure of glasses
Contact: Christian Certa, M.Sc. | Forckenbeckstr. 33 | Tel.: 0241/8047980 | E-Mail: [email protected]
Calculation of Q-value (NBOs) based on glass composition
Oxide Mol-% Element Amount (mol)
SiO2 70 Si4+ 70
Na2O 7 Na+ 14
CaO 3 Ca2+ 3
Al2O3 20 Al3+ 40
∑ 100

Charge Deficit Tetrahedra 20

NBO/T-ratio 0.67 Q-Value 3.33
Non-bridging oxygens 60 molar amoun ts molar amoun ts
molar amoun ts

9 of 12 Lecture: Mineral Materials I | Dr. Philipp Jacobs | Chair of Glass and Glass-Ceramics | WS 2024/2025
Exercise: Structure of glasses
Contact: Christian Certa, M.Sc. | Forckenbeckstr. 33 | Tel.: 0241/8047980 | E-Mail: [email protected]
Constitutional phases in standard glass 74-10-16

Draw the structural formulas to the constitutional phases of the standard glass 74-10-16.

Constitutional Phases
SiO2
Na2O·2SiO2
Na2O·3CaO·6SiO2
SiO2 Na2O·2SiO2

O O- Na+
O Si O 2x O Si O
O O

10 of 12 Lecture: Mineral Materials I | Dr. Philipp Jacobs | Chair of Glass and Glass-Ceramics | WS 2024/2025
Exercise: Structure of glasses
Contact: Christian Certa, M.Sc. | Forckenbeckstr. 33 | Tel.: 0241/8047980 | E-Mail: [email protected]
Constitutional phases in standard glass 74-10-16

Draw the structural formulas to the constitutional phases of the standard glass 74-10-16.

Constitutional Phases
SiO2
Na2O·2SiO2
Na2O·3CaO·6SiO2
Na2O·3CaO·6SiO2

O- Na+ O- Ca2+ O

2x O Si O +3x O Si O- + O Si O
O O O

11 of 12 Lecture: Mineral Materials I | Dr. Philipp Jacobs | Chair of Glass and Glass-Ceramics | WS 2024/2025
Exercise: Structure of glasses
Contact: Christian Certa, M.Sc. | Forckenbeckstr. 33 | Tel.: 0241/8047980 | E-Mail: [email protected]
Food for thought on structure of glasses

• On which quantity does the formation of the oxide coordination polyhedra depend
significantly?

• What are the steps to calculate the Q-value of a glass?

• Can you check if you have drawn the structural formula correctly by counting the
oxygen atoms?

• Which elements belong to the classical network formers/converters?

12 of 12 Lecture: Mineral Materials I | Dr. Philipp Jacobs | Chair of Glass and Glass-Ceramics | WS 2024/2025
Exercise: Structure of glasses
Contact: Christian Certa, M.Sc. | Forckenbeckstr. 33 | Tel.: 0241/8047980 | E-Mail: [email protected]